CN106009490A - Heterogeneous nucleating agent toughening-modified phenolic resin foam and preparation method thereof - Google Patents

Heterogeneous nucleating agent toughening-modified phenolic resin foam and preparation method thereof Download PDF

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CN106009490A
CN106009490A CN201610540087.0A CN201610540087A CN106009490A CN 106009490 A CN106009490 A CN 106009490A CN 201610540087 A CN201610540087 A CN 201610540087A CN 106009490 A CN106009490 A CN 106009490A
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phenolic resin
resin foam
parts
foam
agent
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CN106009490B (en
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俞科静
王梦蕾
钱坤
孙洁
卢雪峰
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses heterogeneous nucleating agent toughening-modified phenolic resin foam and a preparation method thereof. The preparation method of the foam comprises the following steps of preparing a heterogeneous nucleating agent and preparing the modified phenolic resin foam. According to the method, silane coupling agent modified graphene is added for regulating the foam pore structure; meanwhile, the synergistic effect of graphene nanoparticles is exerted, the defects that phenolic foam is poor in mechanical property, high in brittleness and prone to disengagement are effectively overcome, and wide application of the phenolic foam in the engineering field is promoted.

Description

A kind of phenolic resin foam of heterogeneous nucleation agent toughening modifying and preparation method thereof
Technical field
The present invention relates to Polymer/nano particle foam composite, especially relate to a kind of silane coupler modified The preparation method of Graphene toughening metlbond foam.
Background technology
Phenol formaldehyde foam is a kind of novel green insulation material the most with fastest developing speed, is widely used in civil construction, stone The fields such as oil conveyance conduit, military project, Aero-Space.But due to after phenolic resin curing between phenyl ring by single Asia Methyl is connected, and lacks flexible group, and this structure causes that rigid radical density is excessive, chain link rotary freedom Little, thus cause fragility high, the efflorescence frangible, easy of its foamed product, seriously constrain answering of phenol formaldehyde foam With scope and service life.Therefore it is carried out toughening modifying research, prepare that fragility is little, be difficult to powder The high-performance pnenolic aldehyde foam changed, improves the application of phenol formaldehyde foam, has important theory and realistic meaning.
The foam of phenol formaldehyde foam is to be supported by polymer mesh skeleton, forms the most spherical or polygon between skeleton Foam structure.Therefore, the performance of phenol formaldehyde foam is mainly affected by phenolic resin performance and foam structure. In the toughening modifying of phenol formaldehyde foam is studied, nano-material modified it is to improve the expandable and real of phenolic resin Existing phenol formaldehyde foam functionalization and the effective means of high performance.The addition of nano material both can be to resin matrix Play enhancing, toughness reinforcing effect, can effectively prevent again abscess from rupturing when increasing, be distributed in simultaneously Nanoparticle in resin matrix can play good induction nucleating effect as nucleator, causes a large amount of abscess Formed thus obtain fine and closely woven uniform, the nano combined expanded material of excellent comprehensive mechanical property of abscess.
Research finds the bigger serface of two-dimensional graphene, the surface irregularity of Nano grade so that it is induce into Core effect is more notable than one-dimensional CNT, in foamed forming process, is more likely to cell nucleation, Form substantial amounts of abscess, it is thus achieved that aperture is little and uniform cell structure, so that the mechanical property of phenol formaldehyde foam Significantly improve.And the scattering problem that Graphene is in resin matrix is the key technology in foaming process.Pass through Surface modification introduces active function groups, can not only improve the dispersibility of particle, increase the table of Graphene simultaneously Face energy, reduces the surface barrier overcome needed for cell nucleation, is more likely formed little and homogeneous foam structure, carries The mechanical property of high phenol formaldehyde foam.
Summary of the invention
The problems referred to above existed for prior art, the applicant provides a kind of heterogeneous nucleation agent toughening modifying Phenolic resin foam and preparation method thereof.The inventive method by add silane coupler modified after Graphene Regulation and control foam structure, plays the synergism of this nanoparticle of Graphene simultaneously, is effectively improved phenol formaldehyde foam Poor mechanical property, fragility great Yi is fallen the shortcoming of slag, is promoted its extensive application in engineering field.
Technical scheme is as follows:
The phenolic resin foam of a kind of heterogeneous nucleation agent toughening modifying, the preparation method of this foam includes walking as follows Rapid:
(1) preparation of heterogeneous nucleation agent:
1. according to the ratio that concentrated sulphuric acid and concentrated nitric acid volume ratio are 1:1, Graphene is oxidized to graphene oxide；
2. by graphene oxide, dehydrant ultrasonic disperse is in anhydrous tetrahydro furan, the most under nitrogen protection, It is added dropwise over silane coupler, under the conditions of 50～70 DEG C, stirs 10～30h, prepare black product；
3. by step 2. gained black product centrifuge washing, it is dried in 60～90 DEG C of baking ovens, grinds fully, system Obtain the graphene oxide of grafted silane coupling agent, be described heterogeneous nucleation agent；
(2) preparation of modified phenolic resin foam:
1. expandable phenolic resin 100 parts, toughener 3～5 parts, surfactant 1～4 parts, foaming agent are weighed 4～8 parts；
2. by heterogeneous nucleation agent 10～15 parts of ultrasonic disperse in the hydroxy silicon oil of 10～15 parts 5～10 hours, then At ambient temperature, its dispersion liquid is stirred with the most described raw material machinery under conditions of rotating speed 2000～3000rmp Mix 6～12h, be allowed to mix homogeneously；
The most then in mixed system, add acid curing agent 10～20 parts, stir under 2000～3000rpm rotating speeds Pour into rapidly in the foaming mould having been warmed up after Jun Yun, be placed in foaming in 50～90 DEG C of baking ovens 20～40min, prepare the phenolic resin foam of described heterogeneous nucleation agent toughening modifying.
Described in described step (1), dehydrant is the one in calcium oxide, phosphorus pentoxide, DCC, EDCI Or it is multiple；Described silane coupler is one or more in KH550, KH570, KH560, Si563.
In described step (1), the mass ratio between graphene oxide, dehydrant, silane coupler is 1:1～2.5:0.01～0.1.
In described step (2), toughener is PEG200, PEG400 or ethylene glycol.
In described step (2), the hydroxy silicon oil mass parts in dispersible is expandable phenolic resin 10%～15%, molecular weight is 10000～20000.
In described step (2), foaming agent is the one in pentane, isopentane, normal hexane, isohexane or many Kind；Described acid curing agent is one or more in phenolsulfonic acid, phosphoric acid, paratoluensulfonyl chloride.
Useful the having the technical effect that of the present invention
(1) graphene oxide of silane coupler of the present invention grafting has less angle of wetting, becomes based on classics Nuclear theory, this heterogeneous nucleation agent makes the free energy overcome needed for nucleation less, and nucleation rate is bigger, more Easily form homogeneous small cells, it is achieved the raising of phenol formaldehyde foam mechanical property.
(2) present invention selects heterogeneous nucleation agent modified phenolic foam to be due to Graphene distinctive two-dimensional geometry machine Structure gives its effect strengthening skeleton, and the Graphene bearing payload segment is distributed in cataphracted pilotaxitic texture, The effect strengthening matrix can be effectively played, so that the mechanical property of resin matrix is significantly improved； It addition, the specific surface area that Graphene is big, lamella edge defect is more, easily modified；Graphene is again a kind of black Absorber, reduces the conduction of heat of material, gives the more preferable thermal properties of resin-based materials such as phenol formaldehyde foam.
Accompanying drawing explanation
Fig. 1 is the image that the phenol formaldehyde foam in embodiment 1 amplifies 50 times under the microscope.
In figure: (A) unmodified phenol formaldehyde foam；(B) add 10% Graphene/KH550 hybrid material to change The phenol formaldehyde foam of property.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, the present invention is specifically described.
Embodiment 1
The phenolic resin foam of a kind of heterogeneous nucleation agent toughening modifying, the preparation method of this foam includes walking as follows Rapid:
(1) preparation of heterogeneous nucleation agent:
1. it is 1:1 according to concentrated sulphuric acid (mass concentration is 98%) and concentrated nitric acid (mass concentration is 68%) volume ratio Ratio Graphene is oxidized to graphene oxide；
2. by 100mg graphene oxide, 100mg calcium oxide ultrasonic disperse 1h in anhydrous tetrahydro furan, with After under nitrogen protection, be added dropwise over 2.5mg KH550, under the conditions of 50 DEG C, stir 10h, prepare black produce Thing；
3. by step 2. gained black product centrifuge washing, it is dried in 60 DEG C of baking ovens, grinds fully, prepare and connect The graphene oxide of branch silane coupler, is described heterogeneous nucleation agent；
(2) preparation of modified phenolic resin foam:
1. expandable phenolic resin 100 parts, PEG200 3 parts, methyl-silicone oil 1 part, pentane 4 parts are weighed；
2. by 10 parts of ultrasonic disperse of heterogeneous nucleation agent in the hydroxy silicon oil (molecular weight is 10000) of 10 parts 5 Hour, more at ambient temperature, by its dispersion liquid and the most described raw material machine under conditions of rotating speed 2000rmp Tool stirring 6h, is allowed to mix homogeneously；
The most then in mixed system, add phenolsulfonic acid 10 parts, fall rapidly after stirring under 2000rpm rotating speed Enter to have been warmed up, in the foaming mould of (preheating temperature is 75 DEG C), to be placed in foaming 20min in 50 DEG C of baking ovens, Prepare the phenolic resin foam of described heterogeneous nucleation agent toughening modifying；Each raw materials by weight portion meter.
Fig. 1 is the image that the phenol formaldehyde foam in embodiment 1 amplifies 50 times under the microscope, shows in scanning electron microscope The phenol formaldehyde foam going out modification has more homogeneous small cells.
Embodiment 2
The phenolic resin foam of a kind of heterogeneous nucleation agent toughening modifying, the preparation method of this foam includes walking as follows Rapid:
(1) preparation of heterogeneous nucleation agent:
1. it is 1:1 according to concentrated sulphuric acid (mass concentration is 98%) and concentrated nitric acid (mass concentration is 68%) volume ratio Ratio Graphene is oxidized to graphene oxide；
2. by 100mg graphene oxide, 250mg DCC ultrasonic disperse 1.5h in anhydrous tetrahydro furan, with After under nitrogen protection, be added dropwise over 1mg KH560, under the conditions of 70 DEG C, stir 30h, prepare black produce Thing；
3. by step 2. gained black product centrifuge washing, it is dried in 90 DEG C of baking ovens, grinds fully, prepare and connect The graphene oxide of branch silane coupler, is described heterogeneous nucleation agent；
(2) preparation of modified phenolic resin foam:
1. expandable phenolic resin 100 parts, ethylene glycol 5 parts, Tween 80 4 parts, normal hexane 8 parts are weighed；
2. by 15 parts of ultrasonic disperse of heterogeneous nucleation agent in the hydroxy silicon oil (molecular weight is 2000) of 15 parts 10 Hour, more at ambient temperature, by its dispersion liquid and the most described raw material machine under conditions of rotating speed 3000rmp Tool stirring 12h, is allowed to mix homogeneously；
The most then in mixed system, paratoluensulfonyl chloride 20 parts is added, after stirring under 3000rpm rotating speed Pour into rapidly in the foaming mould having been warmed up (preheating temperature is 75 DEG C), be placed in 90 DEG C of baking ovens and be foamed into Type 40min, prepares the phenolic resin foam of described heterogeneous nucleation agent toughening modifying.
Embodiment 3
The phenolic resin foam of a kind of heterogeneous nucleation agent toughening modifying, the preparation method of this foam includes walking as follows Rapid:
(1) preparation of heterogeneous nucleation agent:
1. it is 1:1 according to concentrated sulphuric acid (mass concentration is 98%) and concentrated nitric acid (mass concentration is 68%) volume ratio Ratio Graphene is oxidized to graphene oxide；
2. by 80mg graphene oxide, 160mg calcium chloride ultrasonic disperse 1h in anhydrous tetrahydro furan, subsequently Under nitrogen protection, it is added dropwise over 5.6mg KH560, under the conditions of 70 DEG C, stirs 15h, prepare black product；
3. by step 2. gained black product centrifuge washing, it is dried in 65 DEG C of baking ovens, grinds fully, prepare and connect The graphene oxide of branch silane coupler, is described heterogeneous nucleation agent；
(2) preparation of modified phenolic resin foam:
1. expandable phenolic resin 100 parts, PEG400 4 parts, methyl-silicone oil 2 parts, isohexane 6 parts are weighed.
2. by 12 parts of ultrasonic disperse of heterogeneous nucleation agent in the hydroxy silicon oil (molecular weight 18000) of 11 parts 7 little Time, more at ambient temperature, by its dispersion liquid and the most described raw material machinery under conditions of rotating speed 2500rmp Stirring 8h, is allowed to mix homogeneously；
The most then in mixed system, add phenolsulfonic acid 15 parts, fall rapidly after stirring under 2500rpm rotating speed Enter to have been warmed up, in the foaming mould of (preheating temperature is 75 DEG C), to be placed in foaming 40min in 80 DEG C of baking ovens, Prepare the phenolic resin foam of described heterogeneous nucleation agent toughening modifying.

Claims (6)

1. the phenolic resin foam of a heterogeneous nucleation agent toughening modifying, it is characterised in that the preparation side of this foam Method comprises the steps:
(1) preparation of heterogeneous nucleation agent:
1. according to the ratio that concentrated sulphuric acid and concentrated nitric acid volume ratio are 1:1, Graphene is oxidized to graphene oxide；
2. by graphene oxide, dehydrant ultrasonic disperse is in anhydrous tetrahydro furan, the most under nitrogen protection, It is added dropwise over silane coupler, under the conditions of 50～70 DEG C, stirs 10～30h, prepare black product；
3. by step 2. gained black product centrifuge washing, it is dried in 60～90 DEG C of baking ovens, grinds fully, system Obtain the graphene oxide of grafted silane coupling agent, be described heterogeneous nucleation agent；
(2) preparation of modified phenolic resin foam:
1. expandable phenolic resin 100 parts, toughener 3～5 parts, surfactant 1～4 parts, foaming agent are weighed 4～8 parts；
2. by heterogeneous nucleation agent 10～15 parts of ultrasonic disperse in the hydroxy silicon oil of 10～15 parts 5～10 hours, then At ambient temperature, its dispersion liquid is stirred with the most described raw material machinery under conditions of rotating speed 2000～3000rmp Mix 6～12h, be allowed to mix homogeneously；
The most then in mixed system, add acid curing agent 10～20 parts, stir under 2000～3000rpm rotating speeds Pour into rapidly in the foaming mould having been warmed up after Jun Yun, be placed in foaming in 50～90 DEG C of baking ovens 20～40min, prepare the phenolic resin foam of described heterogeneous nucleation agent toughening modifying；Each raw materials by weight portion Meter.
Phenolic resin foam the most according to claim 1, it is characterised in that described in described step (1) Dehydrant is one or more in calcium oxide, phosphorus pentoxide, DCC, EDCI；Described silane coupler For one or more in KH550, KH570, KH560, Si563.
Phenolic resin foam the most according to claim 1, it is characterised in that oxidation in described step (1) Mass ratio between Graphene, dehydrant, silane coupler is 1:1～2.5:0.01～0.1.
Phenolic resin foam the most according to claim 1, it is characterised in that toughness reinforcing in described step (2) Agent is PEG200, PEG400 or ethylene glycol.
Phenolic resin foam the most according to claim 1, it is characterised in that will change in described step (2) Graphene after property and hydroxy silicon oil carry out dispersion and obtains finely dispersed dispersion liquid, the quality of hydroxy silicon oil Part is the 10%～15% of expandable phenolic resin, and hydroxy silicon oil molecular weight is 10000～20000.
Phenolic resin foam the most according to claim 1, it is characterised in that foaming in described step (2) Agent is one or more in pentane, isopentane, normal hexane, isohexane；Described acid curing agent is benzene One or more in phenol sulfonic acid, phosphoric acid, paratoluensulfonyl chloride.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106928646A (en) * 2017-03-09 2017-07-07 南通山剑石墨设备有限公司 A kind of Graphene phenol-formaldehyde resin modified and preparation method thereof
CN108250666A (en) * 2018-01-18 2018-07-06 同济大学 A kind of amino trimethylene phosphonic salt load graphene oxide activeness and quietness phenolic foam material and preparation method thereof
CN108676198A (en) * 2018-03-30 2018-10-19 北华大学 The preparation method of surface modified graphene oxide and its composite material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103087345A (en) * 2013-01-29 2013-05-08 山东圣泉化工股份有限公司 Preparation method of phenolic foam
CN105601979A (en) * 2016-01-28 2016-05-25 江南大学 Method for preparing phenolic foam containing expanded graphite

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103087345A (en) * 2013-01-29 2013-05-08 山东圣泉化工股份有限公司 Preparation method of phenolic foam
CN105601979A (en) * 2016-01-28 2016-05-25 江南大学 Method for preparing phenolic foam containing expanded graphite

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JINTANG ZHOU ET AL.: "Fabrication and Mechanical Properties of Phenolic", 《POLYMER COMPOSITES》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106928646A (en) * 2017-03-09 2017-07-07 南通山剑石墨设备有限公司 A kind of Graphene phenol-formaldehyde resin modified and preparation method thereof
CN108250666A (en) * 2018-01-18 2018-07-06 同济大学 A kind of amino trimethylene phosphonic salt load graphene oxide activeness and quietness phenolic foam material and preparation method thereof
CN108676198A (en) * 2018-03-30 2018-10-19 北华大学 The preparation method of surface modified graphene oxide and its composite material

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